Functionalized porous membranes and methods of manufacture and use

ABSTRACT

A functionalized microporous, mesoporous, or nanoporous membrane, material, textile, composite, laminate, or the like, and/or a method of making or using such functionalized membranes. The functionalized porous membrane may be a functionalized microporous, mesoporous, or nanoporous membrane that has a functional molecule attached, such as a functional polymer, to the surface and/or internal fibrillar structure of the membrane.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and benefit of U.S. ProvisionalApplication No. 61/992,264 filed May 13, 2014, which is herebyincorporated herein by reference in its entirety.

FIELD OF INVENTION

The instant application relates to new or improved porous membranes,materials, textiles, composites, laminates, and/or methods ofmanufacture and/or use thereof. In at least selected embodiments, theporous membrane may be a functionalized microporous, mesoporous, ornanoporous membrane that has a functional molecule attached, such as afunctional polymer, to the surface and/or internal fibrillar structureof the membrane.

BACKGROUND

Microporous membranes are known and can be made by various processes,and the process by which the membrane is made may have a material impactupon the membrane's physical attributes. See, Kesting, R., SyntheticPolymeric Membranes, A structural perspective, Second Edition, JohnWiley & Sons, New York, N.Y., (1985). Three commercially viableprocesses for making microporous membranes include: the dry-stretchprocess (also known as the CELGARD® process), the wet process, and theparticle stretch process.

The dry-stretch process refers to a process where pore formation resultsfrom stretching a nonporous precursor. See, Kesting, Ibid. pages290-297, incorporated herein by reference. The dry-stretch process isdifferent from the wet process and particle stretch process. Generally,in the wet process, also known as the phase inversion process, or theextraction process or the TIPS process (to name a few), the polymericraw material is mixed with a processing oil (sometimes referred to as aplasticizer), this mixture is extruded, and then, the processing oil isremoved (these films may be stretched before or after the removal of theoil). See, Kesting, Ibid. pages 237-286, incorporated herein byreference. Generally, in the particle stretch process, the polymeric rawmaterial is mixed with particulate, this mixture is extruded, and poresare formed during stretching when the interface between the polymer andthe particulate fractures due to the stretching forces. See, U.S. Pat.Nos. 6,057,061 and 6,080,507, incorporated herein by reference.

Moreover, the membranes arising from these processes may be physicallydifferent and the process by which each is made may distinguish onemembrane from the other. Dry-stretch membranes may, in some instances,have slit shaped pores due to stretch in the machine direction. However,dry-stretch membranes may also be formed that have substantiallyround-shaped pores due to various stretching processes, such as machinedirection stretching and transverse direction stretching. Wet processmembranes may have, in some instances, rounder pores due to stretch inthe transverse machine direction. Particle stretched membranes, on theother hand, may be filled with particulate needed for pore formation andmay have elongated oval shaped pores. Accordingly, each membrane may bedistinguished, in some instances, from the other by its method ofmanufacture.

While membranes made by the dry-stretch process have met with excellentcommercial success, there is a need to improve their physical attributesso that they may be used in an even wider spectrum of applications. Someareas of improvement for such other applications may include pore shapesother than slits and increased transverse direction tensile strength.

U.S. Pat. No. 6,602,593, in some embodiments, is directed to amicroporous membrane, made by a dry-stretch process, where the resultingmembrane has a ratio of transverse direction tensile strength to machinedirection tensile strength of 0.12 to 1.2. In some embodiments in thatdisclosure, the TD/MD tensile ratio is obtained by a blow-up ratio of atleast 1.5 as the precursor is extruded.

U.S. Patent Publication No. 2007/0196638, now U.S. Pat. No. 8,795,565,incorporated herein in its entirety, discloses a microporous membranemade by a dry-stretch process. In some embodiments, the microporousmembrane has substantially round shaped pores and a ratio of machinedirection tensile strength to transverse direction tensile strength inthe range of 0.5 to 5.0. The method of making the foregoing microporousmembrane includes the steps of: extruding a polymer into a nonporousprecursor, and biaxially stretching the nonporous precursor, the biaxialstretching including a machine direction stretching and a transversedirection stretching, the transverse direction including a simultaneouscontrolled machine direction relax.

U.S. Patent Publication No. 2011/0223486, incorporated herein in itsentirety, discloses a microporous membrane made by a dry-stretch processthat has substantially round shaped pores and a ratio of machinedirection tensile strength to transverse direction tensile strength inthe range of 0.5 to 6.0. The method of making the foregoing microporousmembrane may include the steps of: extruding a polymer into a nonporousprecursor, and biaxially stretching the nonporous precursor, the biaxialstretching including a machine direction stretching and a transversedirection stretching, the transverse direction including a simultaneouscontrolled machine direction relax. At least selected embodiments ofsuch membranes were disclosed to be directed to biaxially orientedporous membranes, composites including biaxially oriented porousmembranes, biaxially oriented microporous membranes, biaxially orientedmacroporous membranes, battery separators, filtration media, humiditycontrol media, flat sheet membranes, liquid retention media, and thelike, related methods, methods of manufacture, methods of use, and thelike.

Therefore, there is clearly an unmet need to develop new or improvedmicroporous membranes that provide unique features for certainapplications, for certain conditions, or the like.

SUMMARY OF THE INVENTION

In accordance with at least selected embodiments, aspects or objects,the present invention may address the above mentioned needs, issues orproblems and may provide new or improved porous, microporous,mesoporous, or nanoporous membranes, materials, textiles, composites,laminates, fibers, or films, new or improved devices or productsincluding these new or improved membranes, materials, textiles,composites, laminates, fibers, or films, such as garments, batteries,cells, consumer electronics, vehicles, or systems, and/or methods ofmanufacture and/or use thereof. Microporous membranes, like the Celgard®membranes discussed in the background section above, that have beenfunctionalized by attaching a functional molecule, such as a functionalpolymer, to the surface and/or internal fibrillar structure of themembrane, may be usable as battery separators, as secondary lithium ionor lithium metal battery separators, or the like, or in other desiredmaterials, textiles, composites, laminates, films, and/or the like.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 includes a graph of trickle charge testing of a coin cell batterymade using a control battery separator.

FIG. 2 includes a graph of trickle charge testing of another coin cellbattery made using a control battery separator.

FIG. 3 includes a graph of trickle charge testing of another coin cellbattery made using a control battery separator.

FIG. 4 includes a graph of trickle charge testing of yet another coincell battery made using a control battery separator.

FIG. 5 includes a graph of trickle charge testing of a coin cell batterymade using a battery separator comprising a functionalized membraneaccording to an embodiment described herein.

FIG. 6 includes a graph of trickle charge testing of another coin cellbattery made using a battery separator comprising a functionalizedmembrane according to an embodiment described herein.

FIG. 7 includes a graph of trickle charge testing of another coin cellbattery made using a battery separator comprising a functionalizedmembrane according to an embodiment described herein.

FIG. 8 includes a graph of trickle charge testing of yet another coincell battery made using a battery separator comprising a functionalizedmembrane according to an embodiment described herein.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with at least selected embodiments, the present inventionprovides new or improved porous, microporous, mesoporous, or nanoporousmembranes, materials, textiles, composites, laminates, fibers, or films,and/or methods of manufacture and/or use thereof. Microporous membranes,such as the Celgard® membranes discussed in the background sectionabove, that have been functionalized by attaching a functional molecule,such as a functional polymer, to the surface and/or internal fibrillarstructure of the membrane, may be usable as battery separators, assecondary lithium ion or lithium metal battery separators, or the like,or in other desired materials, textiles, composites, laminates, films,the like, etc. Various membranes useful in embodiments described hereininclude polyolefin membranes such as membranes comprising polyethylene,polypropylene, polymethylpentene, copolymers thereof, mixtures thereof,and so forth.

Functionalized, as used and described herein, may describe any processof adding or attaching a functional molecule to the surface and/orinternal fibrillar structure of the microporous membrane. For example,and clearly not limited thereto, functionalization may include adding orattaching a functional polymer to the surface and/or internal fibrillarstructure of the microporous membrane. Functionalization of amicroporous membrane may be accomplished by various processes whetherknown or later discovered, including, but not limited to, a plasma vapordeposition process, such as one or more vacuum processes (see U.S.Patent Publication Nos. 2011/0114555 and 2010/0234524, now U.S. Pat. No.8,163,356), and/or one or more atmospheric processes (see U.S. Pat. Nos.8,361,276 and 8,016,894 and U.S. Patent Publication No. 2008/0107822).

The functional molecule added, attached, or functionalized to thesurface and/or internal fibrillar structure (or portions thereof) of themicroporous membrane may be any desired molecule. The functionalmolecule may be a functional polymer, including, but not limited tothose that are readily polymerized via radical processes such as acrylicacid, acryloyl chloride, methacrylic acid, hydroxyethyl acrylate,hydroxyethyl methacrylate, styrene, perfluorostyrene, perfluoroacrylates, semifluoroacrylates, partially fluorinated acrylates, allylamine, vinyl amine, acrylate esters, and the like.

Functionalizing microporous membranes, such as by changing their surfaceproperties, can expand the applications for such membranes and/or makethem function more effectively. Functionalization generally may beaccomplished by attaching a functional molecule, such as a functionalpolymer, to the surface and/or internal fibrillar structure of themembrane. Attaching the functional molecule to the internal fibrillarstructure may be desired or desirable in some cases, such as where thefunctionality is required throughout the structure of the membrane. Inaddition, attaching the functional molecule to the internal fibrillarstructure may increase the durability of the functionality, such as byprotecting the functional molecule from removal by abrasion or bycontact with fluids that do not wet out the membrane. In variousembodiments, the functionalization described herein is able toessentially wrap every surface in the membrane with the desiredfunctionality or modification because the vapor from the vapordeposition treatment can reach interior areas of the membrane that maybe unreachable by more traditional methods of coating or attempting tomodify membranes.

For some microporous membranes, attaching functional molecules to theinternal fibrillar structure is made particularly difficult by the smallpore size of the films. Celgard® membrane pore sizes, for example, mayrange generally, without limitation, from 0.03 μm to 0.2 μm in someinstances, which in some cases is similar in size to the functionalmolecules being inserted into the membrane. Moreover, the ovular shapeof the pores in some uniaxially stretched Celgard® membranes may, insome instances, increase the difficulty of inserting functionalmolecules into the membranes' internal structure. Even when thefunctional molecules can be successfully inserted, they often may blockthe pores and thus may impair the fundamental diffusion behavior orbreathability of the membrane. By way of example only, when functionalmolecules are applied mechanically to a porous membrane via applicationof a traditional coating solution, such an application could lead toclogged pores for the membrane, less than 100% coverage, durabilityissues, and/or the like.

Plasma vapor deposition processes, such as, without limitation, variousvacuum processes and various atmospheric processes have beensurprisingly discovered as an effective means of durably depositingfunctional molecules, such as oleophobic fluoropolymers, onto theinternal fibrillar structure of various porous membranes, such as, byway of example, Celgard® membranes. These vapor deposition processeshave the distinct advantage of introducing the functional molecules tothe film in monomer form, with the polymerization occurring on thesurface of the film or membrane, for example, on the fibril surfaces ofthe film or membrane. As a result, the surface treatment:

-   -   Can be effective because of the high degree of coverage;    -   Can be durable because the surface treatment extends, or can        extend, throughout the thickness of the film and may be        covalently attached to the surface depending on mechanism and        plasma intensity. Thus the modification may not be abraded off        and may be unlikely to be removed via solvation;    -   May not impact the diffusion behavior or breathability of the        film because the treatment may be applied to the fibrils at a        molecular level and thus may have virtually no impact on the        film's porous structure (i.e., the pores may not be blocked by        the functional molecule); and    -   Can be modified with differing monomer species, particularly,        but not limited to, those that are readily polymerized via        radical processes such as acrylic acid, acryloyl chloride,        methacrylic acid, hydroxyethyl acrylate, hydroxyethyl        methacrylate, styrene, perfluorostyrene, perfluoro acrylates,        partially fluorinated acrylates, semifluoroacrylates, allyl        amine, vinyl amine, acrylate esters, and the like.

The ability to functionalize microporous membranes, including Celgard®films, using plasma vapor deposition processes can open various newapplications for these membranes. For example, imparting durableoleophobicity to Celgard® films without meaningfully impacting theirbreathability may provide unique waterproof/breathable membranes, suchas, for example, textile membranes. A durable oleophobic Celgard® filmcould also be used as a breathable barrier membrane in fragrance devicescontaining liquid fragrances, as these breathable barrier membranesallow fragrance vapor to permeate the membrane but retain the liquidfragrance. In addition, durable oleophobicity could be useful in bothflat sheet and hollow fiber (capillary) membranes in various industrialapplications, particularly for anti-fouling or to discourage the passageof low-surface energy fluids. Durable hydrophilicity and otherfunctionality could also enable new medical diagnostic membraneapplications. A wide range of functional molecules can be applied usingthe vapor deposition process. In addition, as stated above, the vapordeposition process is ideally suited to any microporous, mesoporous, ornanoporous membrane. Thus, a wide variety of membrane-functionalizationcombinations can be envisioned, including, without limitation,filtration, industrial and consumer textiles, and industrialseparations.

In various embodiments herein, the functionalized membrane is botholeophobic and hydrophobic in that it does not like oil or water.

The functionalization of the membrane using a vapor deposition processcan be accomplished in either a batch (single-piece) or roll-to-rollprocess. The substrate may include various materials or combinations ofmaterials, including:

-   -   A single layer of microporous, mesoporous, or nanoporous        membrane.    -   A bilayer or multilayer stack of microporous, mesoporous, or        nanoporous membranes.    -   A laminate which incorporates one or more layers of microporous,        mesoporous, or nanoporous membrane. Examples of such laminates        include, but are not limited to, a microporous        waterproof/breathable membrane laminated to a woven, nonwoven,        or knit fabric, such as for waterproof/breathable outerwear.        Such laminates can be constructed in 2-layer (membrane+outer        shell fabric), 2.5 layer (printed membrane+outer shell fabric),        and/or 3-layer (inner lining fabric+membrane+outer shell fabric)        formats.

EXAMPLES Example 1

Table 1 below represents the increased oil repellency with minimallyimpaired air permeability of various exemplary Celgard® microporousmembranes that were functionalized with various plasma vapor depositionprocesses (in the Gurley air permeability test, a lower valuecorresponds to higher air permeability):

TABLE 1 JIS Gurley Oil repellency Plasma Typical JIS Gurley (air beforeOil repellency Vapor (air permeability) permeability) treatment aftertreatment Celgard ® Deposition before treatment after treatment (AATCCTM (AATCC TM Product Method (sec) (sec) 118) 118) EZ2090 Atmospheric50-75 50-75 0 2-6 Process 2400 Atmospheric 494-741 565  0 3-4 Process onone side 2400 Atmospheric 494-741 Infinite (zero air 0 5-8 process onpermeability) both sides EZ3030 Vacuum 20-25 37 0 <3 Process (low rate)EZ3030 Vacuum 20-25 36 0 <3 Process (high rate) EZ2090 Vacuum 50-75 89 09 Process (high rate) EZ3030 Vacuum 20-25 41 0 9 Process (high rate)EZ3030 Vacuum 20-25 28 0 9 Process (medium rate) EZ3030 Vacuum 20-25 250 7-8 Process (low rate)

Example 2

In the Examples below, various samples of Celgard® 2500 microporousmembrane (Celgard® 2500 is a microporous monolayer polypropylenemembrane that is about 25 microns thick) were used as the controlsamples. As the experimental samples, various samples of Celgard® 2500microporous membrane were treated by vacuum plasma depositingfluorinated polymer on the surface of the membranes, with varyingthicknesses. The coating or treatment of fluorinated polymer was addedto only one side of the membrane to form a coated or treated membrane.Data from such deposition is reflected in Table 2 below:

TABLE 2 Fluorinated Polymer Thickness (Å) on Celgard ® 2500 Membrane JISGurley (seconds) 0 (Celgard ® 2500 Membrane, “Control”) (~200)  1641 8402292 1441  1440 Similar to Control (~200)  201 192  390 190  686 1852919 47579 

The sample having the fluorinated polymer thickness of about 1440angstroms had a JIS Gurley value close to the reported JIS Gurley valuefor Celgard® 2500 microporous membrane without coating or treatment.Thus, the “1440” sample was chosen to make battery separators.

Various “1440” coated samples (as well as control Celgard® 2500 samples)were then incorporated into batteries (coin cells) as batteryseparators, and battery tests were performed. During testing, the coatedor treated side of the membrane (the surface or side including thevacuum plasma deposited fluorinated polymer coating or treatment) wasplaced facing the cathode in the battery. The separators were tested todetermine whether oxidation was occurring against a high voltagecathode. Specifically, trickle charge testing was performed at 45° C.for one week. In this trickle charge testing, the coin cells were testedat a high or elevated voltage (potentially an “abusive” voltage for sucha coin cell) where a peak, spike or battery failure during one week(about 168 hours) was expected for both control samples as well asinventive samples, which peaks, spikes or failures represent potentialbattery damage or degradation. The voltage was 4.35 volts (whereas thecathodes for these coin cells were rated to withstand about 3.8-4volts).

FIGS. 1 and 2 illustrate trickle charge testing graphs for two coincells (1 and 2, respectively) made with the control Celgard® 2500membrane as the battery separator. No failure was observed during thesetests. However, for FIGS. 3 and 4, which also illustrate trickle chargetesting graphs for two coin cells, Cells 3 and 6, respectively, madewith the control Celgard® 2500 membrane as the battery separator, thereare current peaks observed at about 140 and 160 hours for Cell 3 (seeFIG. 3) and at about 70 hours for Cell 6 (see FIG. 4). Such currentpeaks could have been expected, as these coin cells are rated for lowervoltage than the 4.35 volts to which they were subjected for thistesting.

FIGS. 5-8 illustrate trickle charge testing graphs for four coin cells(Cells 1, 4, 5, and 6, respectively) made with the functionalized orcoated or treated membrane of the present invention as the batteryseparator. No current peaks or failures were observed during thesetests.

By modifying porous membranes with some form of vapor deposition,whether vacuum processes or atmospheric processes or others, the newmembrane applications could include medical diagnostics, vent media, newopportunities for existing products such as filtration, degassing,gasifying, debubbling, among others.

Battery separator applications could include fluoropolymer materials forhigh voltage cell durability, hydrophilic treatments for enhancedwettability, or things like reactive silane and aluminum vaportreatments for a chemically “frosted” separators.

In accordance with at least selected embodiments, aspects or objects,the present invention may address the above mentioned needs, issues orproblems and may provide new or improved porous, microporous,mesoporous, or nanoporous membranes, materials, textiles, composites,laminates, fibers, or films, new or improved devices or productsincluding these new or improved membranes, materials, textiles,composites, laminates, or films, such as garments, batteries, cells,consumer electronics, vehicles, or systems, and/or methods ofmanufacture and/or use thereof. Microporous membranes, like the Celgard®membranes discussed in the background section above, that have beenfunctionalized by attaching a functional molecule, such as a functionalpolymer, to the surface and/or internal fibrillar structure of themembrane, may be usable as battery separators, as secondary lithium ionor lithium metal battery separators, or the like, or in other desiredmaterials, textiles, composites, laminates, films, and/or the like.

In accordance with at least selected embodiments, aspects or objects,there are provided:

A functionalized microporous, mesoporous, or nanoporous membrane,material, textile, composite, laminate, fiber, or the like.

A functionalized microporous, mesoporous, or nanoporous membrane,material, textile, composite, laminate, or the like as shown anddescribed herein.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the likebeing used as battery separators, secondary lithium ion or lithium metalbattery separators, or the like, or in other desired materials,textiles, composites, laminates, films, or the like.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,including:

a functionalized microporous, mesoporous, or nanoporous membrane.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,including: wherein the functionalized microporous membrane being amicroporous Celgard® membrane.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalized microporous, mesoporous, or nanoporousmembrane includes a functional molecule added or attached to the surfaceand/or internal fibrillar structure of the membrane.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functional molecule being a functional polymer.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functional polymer being those that are readily polymerizedvia radical processes.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functional polymer being selected from the group consistingof: oleophobic fluoropolymers, acrylic acid, acryloyl chloride,methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate,styrene, perfluorostyrene, perfluoro acrylates, semifluoroacrylates,allyl amine, vinyl amine, acrylate esters, and the like.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalized microporous, mesoporous, or nanoporousmembrane being functionalized by a functionalization process.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, or the like, where thefunctionalization process including adding or attaching said functionalmolecule to the surface and/or internal fibrillar structure of themicroporous, mesoporous, or nanoporous membrane.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalization process being a plasma vapor depositionprocess.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the plasma vapor deposition process being a vacuum process.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the plasma vapor deposition process being an atmosphericprocess.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the vapor deposition process introducing the functionalmolecules to the membrane in monomer form, with the polymerizationoccurring on the fibril surfaces of the film.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalizing microporous, mesoporous, or nanoporousmembranes, having changed surface properties.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,having increased durability of the functionality, such as by protectingthe functional molecule from removal by abrasion or by contact withfluids that do not wet out the membrane.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the membrane having pore sized ranging from 0.03 μm to 0.2 μm.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the membrane having ovular shaped pores.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the pores remain open or are not blocked by the functionalmolecule.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalization of the membrane being effective because ofa high degree of coverage.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalization of the membrane being durable because thesurface treatment extends, or can extend, throughout the thickness ofthe film and may be covalently attached to the surface depending onmechanism and plasma intensity, whereby the modification may not beabraded off and may be unlikely to be removed via solvation.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalization of the membrane does not impact thediffusion behavior or breathability of the film because the treatment isapplied to the fibrils at a molecular level and thus has virtually noimpact on the film's porous structure (i.e. the pores may not be blockedby the functional molecule).

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalization of the membrane being modifiable withdiffering monomer species, including those that are readily polymerizedvia radical processes such as acrylic acid, acryloyl chloride,methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate,styrene, perfluorostyrene, perfluoro acrylates, semifluoroacrylates,allyl amine, vinyl amine, acrylate esters, and the like.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionilazation of the membrane imparting durableoleophobicity to the films without meaningfully impacting theirbreathability.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalization of the membrane providing a uniquewaterproof/breathable textile.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalization of the membrane providing durablehydrophilicity.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalization of the membrane enabling new medicaldiagnostic membrane applications.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalization of the membrane providing a wide varietyof membrane-functionalization combinations including filtration,industrial and consumer textiles, and industrial separations.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalization of the membrane being done in a batch(single-piece) or roll-to-roll process.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalized membrane being a single layer of microporous,mesoporous, or nanoporous membrane.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the functionalized membrane being a bilayer or multilayer stackof microporous, mesoporous, or nanoporous membranes.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, or the like, whereinthe functionalized membrane being a laminate which incorporates one ormore layers of microporous, mesoporous, or nanoporous membrane.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,wherein the laminate being a microporous waterproof/breathable membranelaminated to a woven, nonwoven, or knit fabric, such as forwaterproof/breathable outerwear.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, or the like, whereinthe laminate being constructed in 2-layer (membrane+outer shell fabric),2.5 layer (printed membrane+outer shell fabric), and/or 3-layer (innerlining fabric+membrane+outer shell fabric) formats.

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, or the like, havingimproved characteristics as shown or described herein including withoutlimitation:

JIS Gurley Plasma Typical JIS Gurley (air Oil repellency Vapor (airpermeability) permeability) before Oil repellency Deposition beforetreatment after treatment treatment after treatment Method (sec) (sec)(AATCC TM 118) (AATCC TM 118) Atmospheric 50-75 50-75 0 2-6 ProcessAtmospheric 494-741 565  0 3-4 Process on one side Atmospheric 494-741Infinite (zero air 0 5-8 process on permeability) both sides Vacuum20-25 37 0 <3 Process (low rate) Vacuum 20-25 36 0 <3 Process (highrate) Vacuum 50-75 89 0 9 Process (high rate) Vacuum 20-25 41 0 9Process (high rate) Vacuum 20-25 28 0 9 Process (medium rate) Vacuum20-25 25 0 7-8 Process (low rate)

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, or the like, beingused as a breathable barrier membrane in fragrance devices containingliquid fragrances (such as those sold under the Febreze Set & Refreshbrand name).

The above functionalized microporous, mesoporous, or nanoporousmembrane, material, textile, composite, laminate, fiber, or the like,being used in flat sheet and/or hollow fiber (capillary) membranes invarious industrial applications (like for anti-fouling or to discouragethe passage of low-surface energy fluids).

A method of making a functionalized microporous, mesoporous, ornanoporous membrane, material, textile, composite, laminate, fiber, orthe like.

A method of making a functionalized microporous, mesoporous, ornanoporous membrane, material, textile, composite, laminate, fiber, orthe like as shown and described herein.

A method of making a functionalized microporous, mesoporous, ornanoporous membrane, material, textile, composite, laminate, fiber, orthe like comprising the steps of:

-   -   functionalizing the membrane with a functional molecule.

The above method of making a functionalized microporous, mesoporous, ornanoporous membrane, material, textile, composite, laminate, fiber, orthe like, wherein the step of functionalizing the membrane with afunctional molecule being by a functionalization process.

The above method of making a functionalized microporous, mesoporous, ornanoporous membrane, material, textile, composite, laminate, fiber, orthe like, where the functionalization process including adding orattaching said functional molecule to the surface and/or internalfibrillar structure of the microporous, mesoporous, or nanoporousmembrane.

The above method of making a functionalized microporous, mesoporous, ornanoporous membrane, material, textile, composite, laminate, fiber, orthe like, wherein the functionalization process being a plasma vapordeposition process.

The above method of making a functionalized microporous, mesoporous, ornanoporous membrane, material, textile, composite, laminate, fiber, orthe like, wherein the plasma vapor deposition process being a vacuumprocess.

The above method of making a functionalized microporous, mesoporous, ornanoporous membrane, material, textile, composite, laminate, fiber, orthe like, wherein the plasma vapor deposition process being anatmospheric process.

The above method of making a functionalized microporous, mesoporous, ornanoporous membrane, material, textile, composite, laminate, fiber, orthe like, wherein the vapor deposition process introducing thefunctional molecules to the membrane in monomer form, with thepolymerization occurring on the fibril surfaces of the film.

In accordance with selected embodiments, a functionalized microporous,mesoporous, or nanoporous membrane, material, textile, composite,laminate, fiber, or the like, and/or a methods of making or using suchfunctionalized membranes are provided. The functionalized porousmembrane may be a functionalized microporous, mesoporous, or nanoporousmembrane that has a functional molecule attached, such as a functionalpolymer, to the surface and/or internal fibrillar structure (or portionsthereof) of the membrane.

The present invention may be embodied in other forms without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the invention.Additionally, the invention illustratively disclosed herein suitably maybe practiced in the absence of any element which is not specificallydisclosed herein.

The invention claimed is:
 1. A functionalized porous membranecomprising: a microporous, mesoporous, or nanoporous membrane having asurface and an internal fibrillar structure, and a functional moleculeattached by a plasma vapor deposition process to: the surface of themembrane, the internal fibrillar structure of the membrane, or acombination thereof, and the functional molecule is a fluorinatedpolymer, wherein the functionalized membrane has, when compared to thesame membrane that does not have the plasma vapor deposited functionalmolecule, an equivalent or better air permeability as measured by JISGurley, and an increased oil repellency as measured by AATCC TM
 118. 2.A battery separator comprising the functionalized membrane according toclaim
 1. 3. The functionalized porous membrane according to claim 1wherein the membrane comprises one or more polyolefins.
 4. Thefunctionalized porous membrane according to claim 1 wherein thefunctional molecule is a polymer polymerized via one or more radicalprocesses.
 5. The functionalized porous membrane according to claim 4,wherein the functional molecule further comprises a polymer selectedfrom the group consisting of: oleophobic fluoropolymers, acrylic acid,acryloyl chloride, methacrylic acid, hydroxyethyl acrylate, hydroxyethylmethacrylate, styrene, perfluorostyrene, perfluoro acrylates,semifluoroacrylates, partially fluorinated acrylates, allyl amine, vinylamine, acrylate esters, and combinations thereof.
 6. The functionalizedporous membrane according to claim 1 wherein the plasma vapor depositionprocess is a vacuum process.
 7. The functionalized porous membraneaccording to claim 1 wherein the plasma vapor deposition process is anatmospheric process.
 8. The functionalized porous membrane according toclaim 1 wherein the plasma vapor deposition process introduces afunctional monomer, with polymerization occurring on the surface and/orthe internal fibrillar structure of the membrane.
 9. The functionalizedporous membrane according to claim 1 wherein the functionalizationprocess increases durability of the functional molecule on the membrane.10. The functionalized porous membrane according to claim 1 wherein themembrane comprises pores and wherein said pores remain open or are notblocked by the functional molecule.
 11. The functionalized porousmembrane according to claim 1 wherein the functionalization processimparts durable oleophobicity to the membrane.
 12. The functionalizedporous membrane according to claim 1 wherein the functionalized membraneprovides a waterproof/breathable textile.
 13. The functionalized porousmembrane according to claim 1 wherein the functionalization processimparts durable hydrophilicity to the membrane.
 14. The functionalizedporous membrane according to claim 1 wherein the functionalizationprocess is a batch (single-piece) process, a roll-to-roll process, or acombination thereof.
 15. The functionalized porous membrane according toclaim 1 wherein the functionalized membrane is a single layer membrane.16. The functionalized porous membrane according to claim 1 wherein thefunctionalized membrane is a bilayer or multilayer membrane.
 17. Thefunctionalized porous membrane according to claim 1 wherein thefunctionalized membrane is a laminate comprising one or more layers ofthe functionalized membrane.
 18. The functionalized porous membraneaccording to claim 17 wherein the laminate includes a woven layer, anonwoven layer, a knit layer, or a combination thereof.